Alternating terpyridine‐endfunctionalized copolymers of styrene and diphenylethylene via anionic polymerization techniques: A detailed characterization study

Abstract

1,1‐Diphenylethylenene (DPE) was copolymerized anionically with styrene to yield well‐defined alternating copolymers, which were terminated by reacting the “living” polymeric carbanion species with 4′‐chloro‐2,2′:6′2″‐terpyridine. DPE containing polymers show improved long‐term service temperatures due to the stiffening of the polymer main chain by the bulky phenyl‐rings. In addition, the functionality provided by the terpyridine group allows the synthesis of attractive materials for various fields of application. The obtained polymers were fully characterized by means of nuclear magnetic resonance, gel permeations chromatography, elemental analysis, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, ultraviolet‐visible spectroscopy, and macromolecular hydrodynamic methods (analytical ultracentrifugation, gel permeation chromatography, intrinsic viscosimetry). In the molar mass range of 2 < M < 25 kg/mol, the scaling relationships between M and hydrodynamic characteristics are obtained. The values of the Kuhn segment length (or persistence length) and hydrodynamic diameters are evaluated and compared with those of linear polystyrene. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3691–3701, 2009

Substituent effects on the stabilities of polymeric and small molecule bis-terpyridine complexes

“…To attach terpyridine ligands to polymer backbones, two main synthetic strategies have been adopted. In a few cases, the nucleophilic aromatic substitution of living anionic polymers to 4 0 -chloro-2,2 0 :6 0 ,2 00 -terpyridine 32,33 (chloro-terpyridine) or terpyridine 34 has been employed, yielding methylene linkages between the polymer chain and the end-capping terpyridine ligand. More commonly, however, an S N Ar reaction of an alkoxide with chloro-terpyridine is employed, yielding either end-functionalized [35][36][37] or side-chain functionalized 30,38,39 polymers with an ether linkage to terpyridine at the 4 0 position.…”

Velocity Sedimentation and Intrinsic Viscosity Analysis of Polystyrene Standards with a Wide Range of Molar Masses

“…[10,11] Also, its capability of estimating extremely small sedimentation coefficients (%0.1 S) was shown by studying cyclodextrin molecules. [12] In the present work, polystyrene standards of narrow molar mass distribution were investigated in a 1 000-fold interval of molar masses, with methyl ethylketone (MEK) as solvent.…”

Hydrodynamic and Molecular Study of Poly{4‐[4‐(hexyloxy)phenyl]ethynylphenyl methacrylate} in Dilute Solutions and Conformational Peculiarities of Brush‐Like Macromolecules

“…The two approaches using differentiation led to virtually identical values of the velocity sedimentation coefficient and, moreover, virtually coincided with the values obtained by the Sedfit program (Figure 2). It was shown in previous investigations that the Sedfit program allows the determination of both the velocity sedimentation coefficient and the frictional ratio for a variety of linear polymer–solvent systems 53–56…”